Part 2:

Impedance Measurements

Purpose of This Note

This application note is part 2 and deals with
electrochemical impedance spectroscopy (EIS)
measurements on dye solar cells.
The effect of various parameters is shown by means of
experiments. Different EIS models are discussed which
can be used to analyze impedance spectra.

Theory
Impedance spectroscopy with dye solar cells
Various electrochemical processes take place in a dye solar
cell (DSC).
By measuring the I-V curves, many important parameters
such as short-circuit current ISC, open-circuit potential
(EOC), Fill factor FF, or cell efficiency h can be determined.
EIS offers additional information about various parameters
of a DSC. When performing an EIS experiment, a specific
point of an I-V curve can be analyzed (see also Figure 1).

Theory
Figure 1 Schematic outline of an impedance
measurement with a DSC

In this experiment, a DC-signal is

applied to the cell which is
superimposed by a small AC-signal
(E dE). The frequency of the
sinusoidal signal is changed during
the experiment and the current
response of the cell is measured (I
dI). The sinusoidal signal has the
same frequency as the applied signal
but its phase is shifted. Both E and I
are used to calculate the
frequency-dependent impedance Z
of the cell.
For detailed analysis, EIS models can
be used to fit the measured curves.
The next sections discuss various EIS
experiments on DSCs and their
analysis.

Experiments
Figure 2 shows various Nyquist
plots of a DSC at different
potentials ranging from 0 V to
0.6 V. The applied AC-signal was
10 mVrms. The frequency range
was varied between 100 kHz and
10 mHz. During the experiment,
a red LED (lem = 625 nm) was
focused on the DSC with a
constant intensity of about 24
mW.

Figure 2 Nyquist diagrams of a DSC at different

potentials. For details, see text.

The shape of the Nyquist plots

depends strongly on the applied
potential. All curves exhibit a large
arc at intermediate frequencies.
The radius of the arc decreases
with increasing potentials.

Figure 3 Detailed illustration of the Nyquist diagram at 0.6 V.

The following sections introduce various EIS

models that can be used to fit the Nyquist
curves shown before. The fit results are used to
describe the electrochemical system of a DSC
for different potential regions more detailed.

A small deformation can be

observed at high frequencies (the
left part of each curve). This
semi-circle is nearly completely
overlapped by the larger arc but it
becomes more distinct at higher
potentials.
Furthermore, an additional
semi-circle appears at potentials
above the open-circuit potential.
Figure 3 shows an enlarged view of
the Nyquist plot at 0.6 V.

Transmission line model

A specific type of EIS model is the transmission line. This model is often used when
electrochemical systems with highly porous electrodes (e.g. TiO2) are investigated. It takes
the stepwise flux of ions within the pores of electrodes into account.
Gamrys Echem AnalystTM includes an editor which allows creating your own custom EIS
models. In addition, various pre-built EIS models can be used instantly and modified if
needed. One pre-built model is called Unified (Figure 4) and resembles a generic form of a
transmission line.

Figure 4 Scheme of the Unified transmission line model. For details, see text.

The model consists of various components which are connected in series and
parallel. The following components are used to describe the electrochemical
system:
ZA Impedance at the outer surface of the electrode. Generally neglected because only
reactions within the pore are taken into account (ZA = ).
ZB Impedance at the back layer (substrate/electrolyte interface). Usually represented as
parallel combination of a charge-transfer resistance (RBL) and constant phase element
(QBL) which describes a non-ideal double-layer capacitance.
r1 Distributed electrolyte resistance within a pore.
r2 Distributed resistance of the semiconductor.
Distributed impedance at the TiO2/dye/electrolyte interface within the pore.
Represented as a parallel combination of a transport resistance (rz) and constant phase
element (qz).
For more information on transmission lines, see
Gamrys application note: Use of Transmission Lines
for Electrochemical Impedance Spectroscopy

EIS models for different potential ranges

The Unified model shown in Figure 4 can be used to describe various cell conditions of a
DSC by adjusting appropriate parameters.
In order to describe the Nyquist diagrams of a whole DSC, the Unified model is extended by
three additional components:

ZCE
RS
W

Counter electrode impedance. Represented as a

parallel combination of a charge-transfer
resistance RCE and a constant phase element QCE.
Series resistance. Represents the sum of bulk
electrolyte, substrate, and electric contact
resistances.
Porous bounded Warburg impedance. Also
referred to as open finite-length diffusion.

Low potentials
As mentioned before, the shape of the Nyquist diagram of a DSC depends on the applied potential.
At low potentials which means near 0 V (short-circuit conditions) the spectrum resembles a
large arc (Figure 2).
We may assume that at very low potentials nearly no electrons are injected into the conduction
band of the semiconductor because the band gap is too large. As a result, the distributed electrode
resistance r2 and the impedance of the TiO2/dye/electrolyte interface are very high. Both
elements thus may be neglected and the lower path of the transmission line drops out of the
model. Instead, the main contribution to the measured impedance results from the back layer of
the anode (ZBL).
In addition, the electrolyte resistance r1 within the pore can be neglected (r1 is set to zero), for
which we assume to be much smaller than r2.

Further, we assume that most reactions occur within the pores because the electrode area within
the pores is much higher compared to the outer surface of the electrode. As a result, ZA is very high
and it can be ignored.
The resulting EIS model for very low potentials is shown in Figure 5. Note that no distributed
elements are used in contrast to the Unified model in Figure 4. The model does in this case not
represent a transmission line.

Low potentials

Figure 5 EIS model of a DSC at low potentials near short circuit conditions. For details, see text.

Low potentials
The small deformation of the Nyquist diagram (Figure 2) at very high frequencies can be
assigned to the counter electrode impedance ZCE. It is very small compared to the large
semicircle resulting from the back layer impedance ZBL which does nearly completely
overlap the semicircle of the counter electrode.
The series resistance RS shifts the whole Nyquist diagram to the right. It can be easily
evaluated as the intersection between x-axis and Nyquist curve at high frequencies.
Diffusion may occur at these low potentials. However, it appears only at very low
frequencies. This makes it impractical to be measured. Hence the diffusion contribution is
ignored during fitting in this note.
Table 1 lists all parameters which were used to fit the Nyquist diagram at 0 V of Figure 2.
Note that the constant phase element is described by an admittance parameter Y and a
dimensionless exponent .

Low potentials
RPt []

YPt [Ss]

Pt

RS []

3.16

3.6310-6

1.0

24.5

RBL []

YBL [Ss]

BL

2.31105

4.1010-6

0.93

Table 1 Parameters used to fit the Nyquist diagram at 0 V of Figure 2

Intermediate potentials
The cells electrochemical behavior changes at potentials below the open-circuit potentials.
We can make some assumptions to build a suitable model for fitting.
The band gap of the semiconductor is now much smaller with increasing potentials.
Electrons can be injected faster into the conduction band. As a result, the impedance of
the TiO2/dye/electrolyte interface as well as the distributed electrode resistance r2 decrease
and need to be taken into account.
In contrast, the back layer impedance ZBL is increasing and its influence to the total
measured impedance is decreasing.
Again, we assume that the distributed electrolyte resistance r1 is much smaller than the
electrode resistance r2. Hence r1 can be set to zero or very small values. Reactions on the
outer electrode surface can be ignored. We assume that ZA is very high.
A schematic diagram of the EIS model for intermediate potentials is shown in Figure 6. Note
that the model represents now a transmission line with distributed elements within the
pore.

Intermediate potentials

Intermediate potentials
The Nyquist diagrams in this potential range (see also Figure 2) show that the
contribution of the impedance at the counter electrode (ZCE) is still small. It is still only
visible as small deformation of the larger semicircle at intermediate frequencies.
The bigger arc which represents the complete transmission line becomes smaller with
increasing potentials. Compared to the measurements at short-circuit conditions,
reactions occur preferably along the electrode within the pore.
The Nyquist curves show at very low frequencies a small deformation. It indicates the
diffusion processes but it can be still not clearly observed in this potential range. The
diffusion element can be added during fitting. However, its fit parameters should be
treated with caution. Much lower frequencies are needed in order to fit the diffusion
element properly.
Table 2 lists all fit parameters for the Nyquist plot at 0.4 V in Figure 2. ZA was fixed at a
very high value during fitting and r1 was set to a very low value. Note that the Warburg
diffusion W is represented by an admittance parameter YW and a time constant B.

Intermediate potentials
RPt []

YPt [Ss]

Pt

RS []

7.46

5.0410-4

0.68

26.3

YW [Ss0.5]

B [s0.5]

1.3610-3

6.7510-3

RBL []

YBL [Ss]

BL

2.71024

6.8810-6

0.45

r []

Y [Ss]

r2 []

8.7510-1

4.8810-1

0.05

34.1

Table 2 Parameters used to fit the Nyquist diagram at 0.4 V of Figure 2.

High potentials
Figure 3 shows the Nyquist diagram of a DSC at 0.6 V. At these high potentials (i.e. above the open-circuit
potential), the high-frequency arc becomes more distinct. The radius of the second arc at intermediate frequencies
decreases further. In addition, a third arc at low frequencies appears. Hence both former models can not be used
anymore for fitting. In order to fit the curve, new assumptions are made to create a suitable EIS model.
The band gap between conduction band and non-conducting valence band decreases further when increasing the
potential. As a result, the conductivity of the semiconductor increases and the electrode transport resistance r2
may be ignored. The distributed resistance r1 of the electrolyte within the pore is again ignored for which we
assume to be much smaller than r2.
Because both transport resistances (r1 and r2) are ignored, the distributed impedance at the TiO2/dye/electrolyte
interface can be combined to a single element. It consists of a single charge-transport resistance RCT in parallel to
a constant phase element QDL representing a non-ideal double-layer capacitance.
We assume that both impedances ZA and ZBL are very high because most reactions occur at the
TiO2/dye/electrolyte interface within the pores. Their influence on the total impedance is very small and both
parameters do not have to be considered in the EIS model.
Figure 7 shows the EIS model used to fit DSCs at high potentials. It fits very well the three arcs of the Nyquist
diagram at 0.6 V shown in Figure 3.
Please note that similar to the experiments at very low potentials no distributed elements are used. The
electrochemical behavior of the DSC at high potentials is described without using transmission lines.

High potentials

Figure 7 EIS model of a DSC at high potentials. For details, see text.

High potentials
The small overlapped arc at high frequencies can be again assigned to the
impedance ZCE of the counter electrode. The second arc at intermediate
frequencies describes the electrochemical behavior at the TiO2/dye/electrolyte
within the pore (RCT and QDL).
The third arc at low frequencies can be assigned to diffusion. It gets more distinct
with increasing potentials. Its contribution to the total impedance can be now
measured as it shifts to higher frequencies.
Table 3 lists all fit parameters which were used to model the Nyquist plot at 0.6 V
of Figure 3.

High potentials
RPt []

YPt [Ss]

Pt

RS []

7.65

2.0810-5

0.82

26.7

YW [Ss0.5]

B [s0.5]

3.7510-1

1.17

RCT []

YDL [Ss]

DL

41.4

5.2810-5

0.84

Table 3 - Parameters used to fit the Nyquist diagram at 0.6 V of Figure 3.

High potentials
The fit results show that the series resistance RS stays nearly constant at about 26
within the entire potential range. The resistance RPt at the platinum counter
electrode increases only a little.
In contrast, the resistance RBL at the back layer of the anode increases drastically
with increasing potentials. This trend is also in agreement with theory. The
conduction band of the semiconductor decreases with increasing potentials
resulting in higher impedances at the back layer.
Note also the difference between the distributed charge-transfer resistance rz and
the single resistance RCT. The first parameter represents a resistance which is
distributed along the inside of the pore. Its value depends also on the pore depth.
RCT represents the resistance of the entire inner electrode surface. Both values are
difficult to compare

Time constants
Figure 8 shows the corresponding Bode plots of the experiments shown above. The
negative imaginary part of the impedance is plotted versus the frequency in a
double-logarithmic style.

Figure 8 Bode plots of -Zimag of a DSC at different potentials. For details, see text.

Time constants
All curves exhibit local maxima at different frequencies f*. The corresponding frequencies are
related to time constants of various electrochemical phenomena by following equation.

The maximum at higher frequencies (indicated with blue arrows) corresponds to the
charge-transfer at the TiO2/dye/electrolyte interface. It shifts to higher frequencies with increasing
potentials. The maximum shifts in this example from 3.2 Hz at 0.4 V to 252 Hz at 0.6 V. Hence the
time constant decreases which means that the rate for the charge-transfer increases. Under
short-circuit conditions (0 V), the maximum is at about 50 mHz. The time constant for the
charge-transfer is very high at such low potentials.
This trend is also consistent with the data gained from the EIS measurements. Most reactions
occur on the back layer of the electrode at short-circuit conditions. With increasing potentials, the
band gap of the semiconductor decreases. Electron injection into the conduction band is favored
over reactions at the back layer of the electrode. As a result, the time constant for the
charge-transfer at the TiO2/dye/electrolyte interface decreases with increasing potentials.
The second maximum (indicated with a red arrow) can in general only be observed at high
potentials and low frequencies. The time constant corresponds to the diffusion process which is
very slow. The maximum is at about 317 mHz for the measurement at 0.6 V.
The maximum shifts down to lower frequencies with decreasing potentials which makes it in
general impractical to measure.

Summary
This application note covers EIS measurements with dye solar cells. Theory about
electrochemical impedance measurements is addressed. Gamrys pre-built
Unified transmission line model is shown and its various components are
discussed.
In addition, theory is applied by means of EIS experiments on DSCs at different
potentials. Nyquist plots are shown and their analysis is explained by using
different EIS models.
Finally, it is discussed how time constants of various electrochemical processes
can be determined by evaluating Bode diagrams.

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Part 1 ~ Dye Sensitized Solar Cells - Basic Principles and Measurements
Part 3 ~ Measuring the Optical Power of your LED
Also available online at Gamry.com/Application-Notes